Production of vat dyestuffs



2,731,464 PRODUCTION OF VAT DYESTUFFS No Drawing. Application September4, 1952,

. Serial No. 307,902

Claims priority, application Germany September 20, 1951 6 Claims. (Cl.260-256.4)

This invention relates to vat dyestuffs of the anthraquinone series, inparticular to amide like compounds of 1-amino-2-acetylanthraquinone.

f We have found that valuable vat dyestuffs are obtained when1-amino-2-acetylanthraquinones which contain an amino group in at leastone further m-position and which may also contain other substituents inthe anthraquinone nucleus, such as halogen atoms, methoxy groups, cyanogroups or hydrocarbon radicals, are condensed to amide like compounds.

This may be effected for, example by reacting the 1- amino--acetylanthraquinones of the said kind either with carboxylic acidhalides or with heterocyclic compounds containing the grouping Halogenat least one in a ring, whichin general behave like carboxylic acidhalides. Both kinds of acylatingl groups,

namely Halogen and i Halogen ultaneously in the molecule of theacylating compound. r

Suitable acylating agents of the said kind'are for example oxalylchloride, fumaryl chloride, chlorfumaryl chloride, benzoyl chlorides,acetyl chloride, propionyl chloride, butyryl chloride, stearicacidchloride, termay also be presentsi United States Patent 0 Thereaction of the 'said acylating agents with the tion, while the aminoing in an inert solvent of high boiling point until no more hydrogenhalide escapes. It is also possible to Work without solvent by combiningthe reactants in a baking process or by allowing the reaction to proceedin an excess of the acylating agent. The co-employment of acid-bindingagents, such as potash, sodium acetate,

sodium sulfite or pyridine, is generally speaking unnecessary, but theiraddition may be of advantage in some cases. The reaction temperaturelies between 70 and 250 C., generally between 120 and 210 C.

The relative proportions are advantageously chosen so that for examplean equivalent of acylating agent reacts on 1 mol ofdiamino-2-acetylanthraqu-inone, for it is preferable to react only theamino group in the 4, 5 or 8 posigroup adjacent to the acetyl group inthe 1-position remains free. The dyestufis thus obtainable are morevaluable than those dyestuffs in which the amino group in l-position 'isalso acylated and which can 1 be obtained by employing a largeramount ofacylating agent and more vigorous reaction conditions. Polyfunctionalacylating components can be reacted with only one mol of, for example,diamino-2-acetylanthraquinone and the other equivalent of the acylatingcomponent saturated by any other amine, as for example by aniline orl-aminoanthraquinone. In this way different amines can be addedsimultaneously or consecutively in any sequence to the reaction mixture.

The dyestuffs obtained dye natural and regenerated cellulose, and alsopolyamides, from a cold or hot vat in ephthaloyl bromide, isophthaloylchloride, chlor isophthaloyl chloride, naphthalene-2,6-dicarboxylic acidchloride, diphenyl4-carboxylic chloride, diphenyl-4,4-dicarboxylicchloride, azobenzene-4,4-dicarboxylic acid chloride, trimesic acidchloride, pyridine-3- and 4-carboxylic acid chloride,quinoline-6-carboxylic acid chloride, anthra- 6,7 benzquinazoline,,2,4-dichlor-6,7-phthaloy1quinazoline,,

2-phenyl-4-chlor-6,7-phthaloylquinazoline, j 2-(an th ra q u i n o n yl-2')-4-chlorquinazoline, l,3-di(4'-chlor- 6',7'phthaloylquinazolyl-2')-benzene, l,4-dichlorphthalazine,4,4'-dichlor-6,6'-diphenyl-1,1'-3,3 bis-dizizine, cyanuric acidchloride, cyanuric acid bromide, trichlorpurine or 2- chlorquinoline4-carboxylic acid chloride.

uniform deep rcd1to black shades of high fasteness tochlorine in whichthey are superior to known dyestuffs of these shades of colour.

The following examples will further illustrate this invention but theinvention is not restricted to these examples. The parts are by weight.

Example 1 28 parts of 1,4-diamino-2-acetylanthraquinone (1 mol) aredissolved hot in 800 parts of o-dichlorbenzene; it is then cooled to C.,14 parts of benzoyl chloride (1 mol) are introduced, the mixture isheated for 2 hours at C. while stirring and then allowed to cool. Thedeposited dyestutf is filtered off by suction, washed with benzene anddried. By careful dissolution in cold concentrated sulfuric acid andprecipitation in ice-water, it is brought into fine dispersion. It dyescotton clear, blue shades fast to chlorine from a brown-red cold vat.

Similar dyestuffs are obtained by employing alkylbenzoylchlorides oralkoxybenzoylchlorides or chlorbenzoylchlorides or brombenzoylchloridesor-diphenyl-4- carboxylicacid chloride or pyridin-3- or 4-carboxylicacid chloride or naphthalene-Z-carboxylic acid chloride instead ofbenzoylchloride.

Example 2 a finely-crystalline blue powder are obtained which bydissolution in and precipitation from concentrated sulfuric acid can bebrought into fine dispersion. The new dyestulf dyes cotton fast blueshades from a brown red vat.

Similar dyestuffs are obtained by replacing isophthaloylchloride byter'ephthaloylchloride or diphenyl-4,4' dicarboxylic acid chloride ornaphthalene-2,6-dicarboxylic acid chloride orazo-benzene-4,4'-dicarboxylic acid chloride.

Example 3 28 parts (.1 mol) of 1,4 diamino 2acetylanthraquinonearedissolvcdinfiOO parts of nitrobenzeneat- 1.30 C. 15 parts of fused,powdered sodium acetate and 27 parts 1 .mol) of:anthraquinonc-Z-carboxylic acid chloride are addedand the mixtureheated 'to boiling for 3 hours while stirring. Itis then allowed to coolto 60 C. and. the deposited dyestuff is filteredoff :by suction andwashed with methanol and water. After drying, 40 parts of a dyestufi areobtained which dyes cotton reddish-blue shades from a hot brown-vat.

Similar dyestuffs are obtained by'ernployin'g instead of anthraquinoneacarboxylic acid-chloride Laminoand 1-nitroanthraquinone-Z-carboxylicacid chloride or 1- aminoor .1nitroor l acylarnino anthraquinone-3carboxylic acid or :1,9-thiazolanthrone-2-carboxylic acid chloride or1-,'9-anthrapyrimidine-Z-carboxylic acid chloride.

Example4 Amixture of 28 parts (1 mol) .of :1,4-diamino-2-ac'etylanthraquinone, 8.1 parts (0.5 mol) of 2,4-dichlor-6-methylpyrimidine and 500 parts of nitrobenzene is heated for v2 hoursat180 C. while stirring. After cooling, the

deposited dyestuif is filtered off by suction, thoroughly washedwithnitrobenzene and then with methanol and dried. 28 parts of adyestuff are obtained which dyes cotton fast blue shades from anolive-green vat.

Example 5 28 parts (1 mol) of1,4-diamino-2-acetylanthraquinonearedissolved in 500 parts of nitrobenzene, then 1 1.2 parts (0.5 mol) of2,4-dichlor 6-phenylpyrimidine are added and the mixture is stirred for2 hours'at 180. C. After working up in the usual way, a dyes'tutfisobtained which dyes cotton clear blue shades fr-ornan olive-green vat.

Example 6 A mixture of 28 parts (l mol) of1,4-diamino-2-acetylanthra'quinone, 11.6 parts (0.5 mol) of2,4,6-trichlor quinazoline and 500 parts of nitro'benzene is heated at'180" C. for 2 hours while-stirring. After working 'up in the usual way,30 parts of a dyestuff are obtained which dyes cotton fast blue shades'frornian olive-green vat. By employing parts. (0.5 mol) of2,4-dichlorquiuazoline instead of 2,4,6-trichlorquinazoline, aifastblue-vat y dyestufi is also obtained. With 1255 parts (0.511101) of2,4-dichlor-6,7 benzquinazoline, a blue-green dyestuffs is obtained. i

' Example 7 quinone and 10 parts (0.5 mol) of dichlorpht'halazine,

there are formed in the said manner 30 parts of a dyestutf which dyescotton currant-colored brown shades.

Example 8 parts of a dyestuff are obtained which dyes cotton powerfulreddish-blue shades from an olive-green vat.

19.9 parts (1 mol) of 2,4-dichlorquinazoline arc'dissloved in 500 ,partsof nitrobenzene. .28 parts (lmol) of 1,4-diamino-2-acetylanthraquinoneare then added in the cold and the whole heateddur'ing the course of anhour to Example 1 0 28 parts (1 mol) of 1,5-diamino2-acetylanthraquinone aredissolved in 700 partsof'nitrobenzene at 130 C.7.6 parts (0.5 mol) of fumaryl chloride are then added and the mixturestirred for 2hours at 180 C. After cooling,

the deposited .dyestufi is filtered off by suction, washed with methanoland dried. 29 parts of a red crystalline dyestufi are obtained whichdyes cotton or polyamide fibres powerful clear red shades from a coldviolet vat.

A similar 'dyestutf isobtained by using the equivalent 0 amount :ofchlorfumaryl chloride, acetyl chloride, propionyl chloride, or butyrylchloride instead of fumaryl chloride.

The hitherto unknown l,S-diamino-Z-acetylanthiaquinone (used as initialmaterial) is prepared as follows:

20 parts of Z-ethyIanthraquinone are dissolved in 250 parts ofmonohydrate at 80 C. Into the'resulting solution, while stirring well,there is allowed to flow during the course of minutes a mixture of 20parts of 98% nitric acid and 80 parts of sulfuric acid. monohydrate.

Towards the end of the introduction, the dinitro compound begins toprecipitate out. The introduction is accelerated so that all thenitrating acid'has been incorporated before the mass becomes viscous.The tempera ture remains at 80 to 85 C. It is stirred for a further 10minutes at this temperature, allowed to cool and the precipitate isfiltered off by suction and the filter cake washed with concentratedsulfuric acid until the filtrate running away is pale yellow, for whichpurpose about A mixture of 28 parts (1 mol) ofl,4-diamino-2-acetylanthraquinone, 6.5 parts (0.35 mol) of cyanurylchloride and 600 parts of;nitrobenzene is heated at, 180'? C. for 2hours while stirring. After the usual working up. 28

200 parts of concentrated sulfuricacid are required. The filter residueis then added to '50 parts of ice-water, heated therein for 15 minutesat C., again filtered by suction, washed until neutral and dried. 7.5parts of 1,5-dinitro- Z-ethYlanthraqdinone are thus obtained as acanaryyellow powder having a melting point of 302 to 303 C. The motherliquor contains the 1,8-dinitro compound which is recovered separately(see Example 19).

10 parts of the l,5-dinitro-2-ethylanthraquinone thus obtained are mixedwith 150 parts of 40% ol'eum while cooling externally. It 'is stirredforlhalf an hour and then 220.parts of 90% sulfuric acid and a solutionof 50 parts of crystallised :iron sulfate in parts of water areadded.Upon stirring on the water-bath, the orange-' yellow color of i theintermediately-forme'd isoxazole disappears and isjreplaced by a browncolor '(I-amino-S- nitro 2-ace'tylan'thraquinone). It is precipitated inicewater, filtered off by suction and washed until neutral. The filtercake, while still moist, is made into a paste with 100 to '200parts ofwater. 15 parts of crystallised sodium sulfide are then added and themixture boiled. By filtering off by suction, washinguntil neutral anddrying there are obtained'8.5 parts of 1,5-diamino-2-acetylanthraquinonein the form a red-brown powder having a melting Epoint of 250 to 252C.,, which acquires a greenish surface lustre when rubbed. The compoundExample 11 28 parts (1 mol) of 1,S-diamino-Lacetylanthraqninone in 800parts of nitrobenzene are heated at 180 C. while stirring for 1 hourswith 10.2 parts (0.5 mol) of a mixture of isophthaloylandterephthaloyl-chlorides 70:30 After the usual working up, 31 parts of adyestufl are obtained which dyes cotton powerful red-brown shades from aBordeaux-violet vat.

With 11.9 parts (0.5 mol) of the chloride of l-chlorisophthalic acid-2,4there is obtained in a corresponding way a dyestufi which dyes cottondull red shades. With 13.7 parts (0.5 mol) of diphenyl-3,3-dicarhoxylicacid chloride there is obtained a dyestufi which dyes cotton fullbluish-red-brown shades Example 12 A mixture of 28 parts (1 mol) of1,5-diamino-2- acetylanthraquinone, 38.8 parts (1 mol) of3,4-phthaloylacridone-7-carboxylic acid chloride and 800 parts ofnitrobenzene is heated for2. hours at 180 C. while stirring. Thedeposited dyestufi is filtered ofi by suction, washed with methanol anddried. 60 parts of. a dyestufi are obtained which dyes cotton powerfulredbrown shades from a black-violet vat.

Example I 4 A mixture of 28 parts (1 mol) of 1,5-diamino-2-acetylanthraquinone, 10 parts (0.5 mol) of 2,4fldichlorquinazoline and500 parts-of nitrobenzene is heated for 2 hours at 180 C. whilestirring. Afterthe usual working up, 32 parts of a dyestuff are obtainedwhich dyes cotton powerful ruby-red shades from a violet vat.

Example A mixture of 28 parts (1 mol) of 1,5-diamino-2-acetylanthraquinone, 700 parts of o-dichlorbenzene and 9.15 parts (0.5mol) of cyanuryl chloride .isheated .for 1.5 hours at 180 C. whilestirring. Then span; (0.54 mol) of aniline are added and the wholestirred for another hour at 180 C. The deposited dyestutf is thenfiltered oii by suctionf'washed well with hot dichlorbenzone and thenwith cold methanol and dried. It dyes cotton entrant-colored shades froma brown-violet vat.

With 11.3 parts (0.5 mol) of 2-chlorquinoline-4-carboxylic acid chloridethere are obtained in a corresponding manner 32 parts of a dyestufiwhich dyes cotton currant-colored red shades 'from 'the vat.

Example 16 A mixture of 32 parts (1 of"1,5-diamino-4-chlor'2-acetylanthraquinone (prepared by;treating the l-amino-5-nitro-2-acetylanthraqinone ofmelting point 294 to 295 vat.

272 C.), 12 parts (0.5 mol)'of isophthaloyl chloride and 500 parts ofnitrobenzene is heated for 2 hours at 180 C. while stirring. After theusual working up, a dyestuff is obtained which dyes cotton beautifulruby-red shades from a violet vat.

A dyestufl giving Bordeaux-red dyeings is obtained in a similar way with2,4dichlorquinazolin1e.

Example 17 A mixture of 29.5 parts (1 mol) of 1,4,5-triamino-2-acetylaminoanthraquinone (prepared from the l-amino-S-nitro-4-chlor-2-acetylanthraquinone described in Example 16 byreaction with p-toluene sulfonamide and saponification of the1-amino-5-nitro-4(p-toluene-sulfonamido)-2-acetylanthraquinone firstobtained to 1,4-diamino-Smitro-2-acetylanthraquinone of melting point255 C. and then reducing this compound with sodium sulfide to1,4,5-triamino-Z-acetylanthraquinone of melting point above 320 C,), 28parts of benzoyl chloride (2 mols) and 800 parts of nitrobenzene isboiled for 3 hours while stirring. The dyestutf of melting point 269 to270 C. separated in the usualway dyes cotton bluegrey shades of verygood fastness properties from a violet Example 18 A mixture of 29.6parts (1 mol) of 1,5-diamino-8- hydroxy-Z-acetylanthraquinone(obtainable by treating the 1,5-dinitro-Z-acetylanthraquinone describedin Example 10 for 2 hours at 20 C. with oleum and further treatment ofthe compound obtained by precipitation with water, consecutively withferrous sulfate and sodium sulfide; dark red-brown crystals whichsublime at about 300 C. with a blue color), 10.1 parts (0.5 mol) ofisophthaloyl chloride and 800 parts of nitrobenzene is heated for 1 /2hours at180 C. while stirring. After the usual working up, 35 parts of aviolet dyestuir are obtained which dyes cotton from the vat brilliantviolet shades which, however, are not fast to washing and chlorine byreason of the free hydroxyl groups contained in the dyestutf.

L Example 19 A mixture of 28 parts (1' mol) of 1,8-diamino-2-acetylanthraquinone, 10.2 parts (0.5 mol) of isophthaloyl chloride and800 parts of nitrobenzene is heated for 1% hours at C. while stirring.After the usual working up, 31 parts of a dyestufi are obtained whichdyes cotton clear ruby-red shades from an olive-black vat.

The abovementioned 1,8-diamino-Z-acetylanthraquinone is obtained fromthe mother liquor containing 1,8- dinitro-2-ethylanthraquinone describedin the penultimate paragraph of Example 10 in a similar manner to thatdescribed for the preparation of1,S-diamino-2-acetylanthraquinone in thesaid Example 10. The 1,8-dinitro-2-acetylanthraquinone first obtainedmelts at 238 C. to 240 C. and the 1,8-diamino-2-acetylanthraquinoneobtained therefrom by consecutive treatment with oleum, ferrous sulfateand sodium sulfide melts at 234 to 235 C.; it forms brown crystals witha green surface lustre.

. Example 20 A mixture of 28 parts of 1,4-diamino-2-acetylanthraquinone(1 mol), 37 parts of 2-phenyl-4-chloro-6,7- phthaloylquinazoline (1 mol)and 800 parts of nitrobenzene is heatedto 180 C. for 3 hours whilestirring. After cooling the precipitated dyestuff is filtered off bysuction, washed with nitrobenzene and methanol'and then dried. There areobtained 61 parts of a dyestutf which dyes cotton green shadesfrom anolive brown vat.

What we claim is p 1. A compound selected from the group consisting of'7 the:mmpoundsphaving thexfollowing structural formulas;

and

2. The ound 3. "The cbmpumid 4. The compound CHr-CO- 5. The compound NH;(n)

CHI-

F O NH CHr-CO 10 6. The compound NH: O I! C1 3 1'11; lZ

0 31 (I? 1\:IH

CH1-OO M NH: 0

References Cited in the file of this patent UNITED STATES PATENTS2,299,141 Hauser Oct. 20, 1942 2,567,821 Moergeli Sept. 11, 1951

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE COMPOUNDS HAVINGTHE FOLLOWING STRUCTURAL FORMULAS: